Patent GB-838994-A (GB)
Title: New anthradipyridazones and their use in polymeric materials
Inventor: IRVING FRANCIS
IPC: C08K5/3465
Filed: 1956-12-05
Abstract: The invention comprises anthra - dipyridazones having the general formula <FORM:0838994/IV (b)/1> wherein X and Y are the same or different and represent hydrogen or a monovalent organic radical such as a -CH2COOH group or an alkyl, hydroxyalkyl, alkoxyalkyl, cycloalkyl, alkyl-cycloalkyl, alkenyl, aralkyl which may be substituted by alkyl or halogen, e.g. chlorine, aryl which may be substituted by alkyl, alkoxy or halogen, e.g. chlorine, or a heterocyclic or alkyl-heterocyclic radical.  The compounds give strongly blue fluorescent solutions and are useful in modifying the colour of textiles and polymeric materials (see Groups IV (a) and IV (c)) and of paints, lacquers and varnish, some being colouring agents and others whitening agents.  They may be prepared by interacting a hydrazine of the formula NH2.NHY with an anthramono-pyridazone of the formula <FORM:0838994/IV (b)/2> wherein X and Y are as defined above and one Z represents hydrogen and the other Z represents a carboxyl group or functional derivative thereof, e.g. an ester, acid chloride, amide or nitrile group, the presence of water being necessary if the second Z represents a nitrile or amido group.  Suitable hydrazines are hydrazine, methyl-, ethyl-, n-butyl-, hydroxy-ethyl- and allyl-hydrazines, hydrazino-acetic acid, phenyl-, a -naphthyl-, p-tolyl-, o-chlorphenyl-, 2 : 5-dichlorophenyl- and 2 : 6-dimethyl phenyl-hydrazines and 3-hydrazino pyridine.  The reaction may be effected by heating, if desired in the presence of a liquid medium such as water, sulphuric acid, oleum, acetic acid or xylene.  The anthra-di-pyridazones, wherein X and Y are identical are preferably formed directly from the appropriate anthraquinone dicarboxylic acid or its functional derivative by interaction with more than one equivalent of the appropriate hydrazine compound without isolation of the monopyridazone intermediate and in the presence of water if the functional p  derivative is a nitrile or amide.  The anthra monopyridazones used in the first method as starting materials may be prepared by reacting anthraquinone- 1 : 5- or -1 : 4-dicarboxylic acid or a functional derivative thereof with a hydrazine NH2.NHX in the presence of one molar proportion of an alkali or an amount of the hydrazine compound insufficient to cause formation of the dipyridazone.  Examples describe the preparations of (1) and (2) 2-(211 : 611-dimethyl phenyl)-8 - n - butylanthra - 11 : 91 (N) : 101 (N) : 51 - dipyridazone; (3) 2 : 8-diphenylanthra-11 : 91 (N): 101 (N) : 51 - dipyridazone; (4) 2 : 8 - di - p - toly anthra - 1 : 91 (N) : 101 (N) - 51 - dipyridazone; (5) 2 : 8 - di - (211 - chlorophenyl) anthra - 11 : 91 (N) : 101 (N) - 51 - dipyridazone; (6) 2 : 8 - di - (211 : 511 - dichlorophenyl) anthra - 11 : 91 (N) : 101 (N) : 51 - dipyridazone; (7) 2 : 8 - dibutyl anthra - 11 : 91 (N) : 101 (N1) : 51 - dipyridazone; (8) 2 : 7 - diphenyl anthra - 11 : 91 (N) : 101 (N) : 41 - dipyridazone; (9) and (24) anthra-11 : 91 (N) : 101 : (N) : 51 - dipyridazone; (10) and (11) 2 : 8-di - (211 : 611 - dimethyl phenyl) anthra - 11 : 91 (N) : 101 (N) - 51 - dipyrisazone; (12) 2 : 8 : di(211 - hydroxyethyl) anthra - 11 : 91 (N) : 101 (N) : 51 - pyridazone; (13) 2-(211 : 611-dimethyl phenyl) - anthra - 11 : 91 (N) : 101 (N) - 5 - dipyridazone; (14) 2 : 8-di-(211 : 611-diethyl phenyl) anthra - 11 : 91 (N) : 101 (N) : 51 - dipyridazone; (15) 2 - (211 : 611 - diethyl phenyl) anthra - 11 : 91 (N) : 101 (N) : 51 - dipyridazone; (16) 2 : 8 - di - (o - bromo phenyl) anthra - 11 : 91 (N) : 101 (N) : 51 - dipyridazone; (17) 2 - (611 - chloro - 211 - methyl phenyl) anthra - 11 : 91 (N) : 101 (N) : 51dipyridazone; (18) and (19) 2-(211 : 611-dichlorophenyl) anthra - 11 : 91 (n) : 101 (N) : 51 - dipyridazone; (2) 2-(211 : 611-dimethyl phenyl)-7-n - butyl anthra - 11 : 91 (N) : 101 (N) : 41 - dipyridazone; (21) 2 : 7-di-n-butyl anthra-11 : 91 (N) : 101 (N) : 4 - dipyridazone; (22) 2 : 7 - di - o - chlorophenyl anthra - 11 : 91 (N) : 101 (N) : 41-dipyrazone; and (23) 2 : 7-di-(211 : 611-dimethyl phenyl) anthra - 11 : 91 (N) : 101 (N) : 4 - dipyridazone, by reaction of an appropriate hydrazine or hydrochloride or hydrate thereof with an appropriate anthra-mono-pyridazone carboxylic acid or in certain cases, where X and Y are the same, by reaction of excess of the appropriate hydrazine or hydrochloride, hydrate or sulphate thereof, with the appropriate anthraquinone carboxylic acid or dinitrile thereof.  The preparation of most of the anthra-monopyridazone carboxylic acid starting materials by the above-described method are given in the corresponding examples. Specification 813,093 is referred to.ALSO:The invention comprises anthradipyridazones having the general formula <FORM:0838994/IV(c)/1> wherein X and Y may be the same or different and represent hydrogen or a monovalent organic radical such as a -CH2COOH group or an alkyl, hydroxyalkyl, alkoxyalkyl, cycloalkyl, alkylcycloalkyl, alkenyl, aralkyl which may be substituted by alkyl or halogen, e.g. chlorine, aryl which may be substituted by alkyl, alkoxy or halogen, e.g. chlorine, or a heterocyclic or alkyl-heterocyclic radical.  The compounds give strongly blue fluorescent solutions and are useful in treating textile materials and in modifying the colour of polymeric materials (see Group IV (a)), some being colouring agents and others whitening agents.  They may be prepared by interacting a hydrazine of the formula NH2.NHY with an anthramonopyridazone of the formula <FORM:0838994/IV(c)/2> wherein X and Y are as defined above and one Z represents hydrogen and the other Z represents a carboxyl group or functional derivative thereof, e.g. an ester, acid chloride, amide or nitrile group, the presence of water being necessary if the second Z represents a nitrile or amide group.  Suitable hydrazines are hydrazine, methyl-, ethyl-, n-butyl-, hydroxyethyl- and allyl-hydrazines, hydrazinoacetic acid, phenyl-, a -naphthyl-, p-tolyl-, o-chlorphenyl-, 2 : 5-dichlorophenyl- and 2 : 6-dimethylphenyl-hydrazines and 3-hydrazinopyridine.  The reaction medium may be water, sulphuric acid, oleum, acetic acid or xylene. Those anthradipyridazones of the above general formul  wherein X and Y are identical are preferably formed directly from the appropriate anthraquinone dicarboxylic acid or functional derivative thereof by interaction with more than one equivalent of the appropriate hydrazine compounds without isolation of the monopyridazone intermediate and in the presence of water if the functional derivative used is a nitrile or an amide.  Examples describe the preparations of: (1) and (2) 2-(211:611-dimethylphenyl) - 8 - n - butylanthra - 11 : 91-(N) : 101 - (N) : 51 - dipyridazone, (3) 2 : 8-diphenylanthra-11 : 91-(N) : 101-(N) 51-dipyridazone, (4) 2 : 8-di-p-tolylanthra-1 : 91-(N) : 101-(N) - 51 - dipyridazone, (5) 2 : 8 - di - (211-chlorophenyl)anthra - 11:91 - (N) : 101-(N) - 51-dipyridazone, (6) 2 : 8 - di - (211:511 - dichlorophenyl)anthra - 11:91 - (N) : 101 - (N) : 51 - dipyridazone, (7) 2 : 8 - dibutylanthra - 11:91-(N) : 101 - (N1) : 51 - dipyridazone, (8) 2 : 7-diphenylanthra - 11:91 - (N) : 101 - (N) : 41 - dipyridazone, (9) and (24) anthra-11:91-(N):101-(N) : 51-dipyridazone, (10) and (11) 2 : 8-di-(211:611 - dimethylphenyl)anthra - 11:91 - (N) : 101 - (N) - 51 - dipyridazone, (12) 2 : 8 - di - (211-hydroxyethyl)anthra - 11:91 - (N) : 101 - (N) : 51 - dipyridazone, (13) 2 - (211:611 - dimethylphenyl)anthra - 11:91 - (N) : 101 - (N) - 5 - di pyridazone, (14) 2 : 8 - di - (211:611 - diethylphenyl)anthra - 11:91 - (N) : 101 - (N) : 51-dipyridazone, (15) 2 - (211:611 - diethylphenyl)-anthra - 11:91 - (N) : 101 - (N) : 51 - dipyridazone, (16) 2 : 8 - di - (o - bromophenyl)anthra-11:91 - (N) : 101 - (N) : 51 - dipyridazone, (17) 2 - (611 - chloro - 211 - methylphenyl)anthra-11:91 - (N) : 101 - (N) : 51 - dipyridazone, (18) and (19) 2 - (211:611 - dichlorophenyl)anthra-11:91 - (N) : 101 - (N) : 51 - dipyridazone, (20) 2 - (211:611 - dimethylphenyl) - 7 - n - butylanthra - 11:91 - (N) : 101 - (N) : 41 - dipyridazone, (21) 2 : 7 - di - n - butylanthra - 11:91-(N) : 101 - (N) : 4 - dipyridazone, (22) 2 : 7-di - o - chlorophenylanthra - 11:91 - (N) : 101-(N) : 41 - dipyrazone, and (23) 2 : 7 - di - (211:611 - dimethylphenyl)anthra - 11:91 - (N) : 101-(N) : 4-dipyridazone, by reaction of an appropriate hydrazine or hydrochloride or hydrate thereof with an appropriate anthra-monopyridazone carboxylic acid or in certain cases, where X and Y are the same, by reaction of an excess of the appropriate hydrazine, or hydrochloride, hydrate or sulphate thereof, with the appropriate anthraquinone carboxylic acid or dinitrile thereof. Examples 25, 26, 27 and 35 describe the treatment of polyethylene terephthalate fabric with an aqueous dispersion containing a dipyridazone of the above kind and a wetting agent, whereby a whitening effect is obtained. Specification 813,093 is referred to.ALSO:Artificial resins, including polyamides, polyesters, polystyrene and cellulose acetate, are treated to modify their colour with anthradipyridazones having the general formula <FORM:0838994/IV (a)/1> in which X and Y may be the same or different and represent hydrogen or a monovalent organic radical such as a -CH2COOH group or an alkyl, hydroxyalkyl, alkoxyalkyl, cycloalkyl, alkylcycloalkyl, alkenyl, aralkyl which may be substituted by halogen, e.g. chlorine, or an alkyl group, aryl which may be substituted by alkyl, alkoxy or halogen, or a heterocyclic or alkylsubstituted heterocyclic radical. The pyridazones give blue fluorescent solutions and some serve as colouring matters and others as whitening agents.  They may be added during the manufacture of the polymeric material or may be added to the polymeric material before it is spun, extruded or otherwise shaped.  Alternatively, films and textile materials may be treated with a solution or suspe